Conversion of Trivalent Uranium Anilido to Tetravalent Uranium Imido Species via Oxidative Deprotonation.

ABSTRACT

Two uranium(III) anilido complexes were synthesized, Tp*2U(NH-C6H4-p-terpyridine) (2-terpy) and Tp*2U(NH-C6H4-p-CH3) (2-ptol), where Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, by protonation of Tp*2UBn (1-Bn; Bn = benzyl) with 4-[2,6-di(pyridin-2-yl)pyridin-4-yl]benzenamine or p-toluidine, respectively. Conversion to the respective uranium(IV) imido species was possible by oxidation and deprotonation, forming Tp*2U(N-C6H4-p-terpyridine) (3-terpy) and Tp*2U(N-C6H4-p-CH3) (3-ptol). These compounds were characterized by multinuclear NMR spectroscopy, IR spectroscopy, electronic absorption spectroscopy, and X-ray crystallography.